EP1816178A1 - Formmassen mit lumineszierenden Pigmenten - Google Patents

Formmassen mit lumineszierenden Pigmenten Download PDF

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Publication number
EP1816178A1
EP1816178A1 EP06002045A EP06002045A EP1816178A1 EP 1816178 A1 EP1816178 A1 EP 1816178A1 EP 06002045 A EP06002045 A EP 06002045A EP 06002045 A EP06002045 A EP 06002045A EP 1816178 A1 EP1816178 A1 EP 1816178A1
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EP
European Patent Office
Prior art keywords
luminescent
smc
resin
molding
molding compound
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English (en)
French (fr)
Inventor
Nicole Busam
Oliver Türk
Giovanni Vargiolu
Simone Weber
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POLYNT GMBH
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Polynt & Co KG GmbH
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Priority to EP06002045A priority Critical patent/EP1816178A1/de
Priority to PCT/EP2007/000869 priority patent/WO2007088055A1/en
Publication of EP1816178A1 publication Critical patent/EP1816178A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V15/00—Protecting lighting devices from damage
    • F21V15/01—Housings, e.g. material or assembling of housing parts

Definitions

  • the present invention relates to a luminescent molding compound.
  • Molding compounds, and in particular sheet molding compounds, henceforth abbreviated as SMC consist mainly of reinforcing fibers (e.g., glass fibers), a thermosetting resin suitable to form a reinforced polymer system with the fibers, usually one or more fillers, thickening agent(s) and mold release agent(s).
  • SMC sheet molding compounds
  • TMC thick molding compounds
  • BMC bulk molding compounds
  • luminescence is the non-thermal emission of light after absorption of energy.
  • the energy absorbed by the luminescent system or material leads to an excited electronic state that possesses a certain lifetime. After this lifetime which is typical for the type of material the system returns to its electronic ground state by emitting light of a certain wavelength.
  • photoluminescence electroluminescence
  • thermoluminescence thermoluminescence
  • chemoluminescence More information about these processes can be found e.g. in Römpp Chemie-Lexikon (Eds. J. Falbe, M. Regitz; Thieme-Verlag, Stuttgart, 1995 ) or common textbooks of physics or chemical physics.
  • Luminescent elastomeric systems have also been described:
  • WO 01/00748 A1 the use of luminescent latex mixtures is taught, e.g. for the production of luminescent balloons and the like. Moreover, said patent describes a luminescent ink suitable for printing on latex articles.
  • luminescent molded articles are produced in processes like hand lay-up, spray-up or resin transfer molding, i.e. in so-called open mold processes where there is no flow of the material in a mold.
  • Producing laminated articles with a luminescent gel coat or the treatment of non-luminescent molded parts with a luminescent paint is a laborious and cost intensive process. Moreover, luminescent paint films are more easily inflammable than molded articles containing flame-retardant fillers.
  • thermosetting molding compounds in particular sheet molding compounds, which can be molded at elevated temperature into inherently luminescent articles with surface quality sufficient for an application as e.g. safety equipment of safety personnel, fire brigade, police and the like, without using requiring additional production steps such as application of luminescent paints or gel coats.
  • SMC self-luminescent sheet molding compound
  • Sheet molding compounds provide fiber reinforced thermosetting resins in a form which allows to process these reinforced resins in a molding process at elevated temperature and pressure in industrial applications where parts can be molded economically in the order of magnitude from several thousands up to several millions of pieces per year.
  • the annual production of SMC is in Europe around 264 000 t/a, in the U.S.A. 292 000 t/a, 194 000 t/a in Asia and worldwide 752 000 t/a.
  • International standard ISO 8605 “Textile glass reinforced plastics - Sheet molding compound (SMC) - Basis for a specification” describes SMC in a classification based on the composition of the material as consisting fundamentally of
  • thermosetting resins i.e. matrix material
  • unsaturated polyesters UP
  • EP epoxy resins
  • PUR polyurethane resins
  • P phenolic resins
  • VE vinyl ester resins
  • UP resins and VE resins are used in the production of SMC.
  • different combinations of bivalent alcohols and bivalent unsaturated acids or the corresponding anhydrides can be used to form unsaturated polyesters by polycondensation: Typical acids or anhydrides used in production of UP resins are
  • Typical vinyl esters are those of the novolac type and those of the bisphenol A type, the basic chemistry of which is known to those skilled in the art.
  • VE resins are mostly used to form SMC for application in parts where temperature resistance and/or chemical resistance is required, e.g. in automotive parts like oil sumps and valve covers for internal combustion engines.
  • Unsaturated polyester or vinyl ester resins are typically dissolved in a monomer possessing a vinyl group like e.g. styrene.
  • the monomer participates in the polymerization reaction of the unsaturated polyester or vinyl ester started by the initiator (radical polymerization).
  • radical polymerization By this copolymerization of the monomer and the thermosetting resin a three dimensional network is formed (crosslinking). Due to the polymerization reaction of the double bonds in the unsaturated polyester and especially the copolymerization of the vinyl group containing monomer (styrene) the cured resin exhibits a shrinkage of about 8-10%.
  • thermosetting resin As reinforcement many materials can be used.
  • the classical way of reinforcing a thermosetting resin is the usage of glass fiber bundles, so called rovings. Until today this is the predominant way of reinforcement of thermosetting resins in SMC, but thermoplastic materials may also be reinforced with glass fibers.
  • glass fiber roving several single filaments of glass fibers having a diameter of approximately 10 to 20 ⁇ m are bound together to form a bundle.
  • the roving may consist of a single bundle or (preferably) of several bundles.
  • the parameters describing the elementary properties of such glass fiber rovings which are the diameter of the elementary fiber, the weight of the bundle per meter, which is expressed by the bundle tex number, and the weight of the complete roving per meter, which is expressed by the tex number of the roving.
  • the tex number is given in milligrams per meter.
  • the fiber diameter of the elementary fiber is preferably in the range of 11 to 16 ⁇ m (for glass fibers).
  • the bundle weight which is given by the bundle tex number is typically in the range of 60-90.
  • the roving weight which is given by the roving tex number is typically 2400 tex but 4800 tex rovings can also be used.
  • the single filaments can only form the above-mentioned bundles by the use of a sizing which is applied onto the glass fibers during their production.
  • the sizing is a liquid mixture of several components like an antistatic agent, a film former, a lubricant, and a silane coupling agent which facilitates the interaction or coupling, respectively, between the glass fiber surface and the unsaturated polyester. Only the sizing ensures the processability of the glass fibers in the SMC process; glass fibers without sizing are not processable due to the formation of fluff. It is evident that the chemical composition and especially the solubility of the sizing determines the defilamentation of the glass fiber bundle in the SMC and/or during molding.
  • a high solubility of the sizing leads to a good defilamentation of the fiber bundles and therefore to good mechanical properties of the molded part.
  • mold flow is adversely affected.
  • a low solubility of the sizing results in poor defilamentation and poor mechanical properties of the molded part while mold flow is facilitated.
  • a very good dispersion of the glass fiber bundles in the SMC is desired - e.g. to achieve a transparent and homogeneous SMC - it is mandatory to use glass fibers with a sizing having a high solubility.
  • glass fiber reinforcements also carbon fibers, aramid fibers (polyamide), basalt fibers (geotextile fibers) or natural fibers like hemp, flax, jute and the like can be used.
  • the reinforcement can also consist of nonwoven (e.g., fleeces) or woven fabrics (multi-layered or single layered) of one or a mixture of two or more types of the above mentioned reinforcement fibers.
  • the thickening process or maturation can be considered to be the fundamental step in the SMC process. Only the thickening makes the SMC an SMC, i.e. an easy to handle and applicable sheet of fiber-reinforced thermosetting resin that is not sticky and can be cut into a desired shape and which can be placed in a mold for molding parts of a desired form at elevated temperature and pressure.
  • the thickening makes use of a reaction of the terminal acid groups of the unsaturated polyester chain with an alkaline earth oxide or hydroxide. By that reaction that can be called a bridging reaction, polyester chains with a higher molecular mass are formed and the viscosity rises accordingly.
  • the viscosity of the resin paste is typically in the range of 10 Pa ⁇ s to 50 Pa ⁇ s.
  • the thickening process increases this viscosity of the resin paste from this level of 10 Pa ⁇ s to 50 Pa ⁇ s (cf. Fig. 1) to a viscosity level of approximately 5 ⁇ 10 4 to 1 ⁇ 10 5 Pa ⁇ s which is usually reached after two days. It gives the SMC a leatherlike appearance and enables the operator to cut the SMC into pieces of desired size, remove the carrier film without resin sticking to the film or to the hands of the operator, and to put the pre-cut SMC sheets into the mold.
  • the viscosity level of the thickened thermosetting resin is lowered again significantly due to the influence of the temperature in the mold. This effect allows the resin paste to flow in the mold and to completely fill the cavity within the comparatively short time of the molding process.
  • the thickening level is too low due to incorrect formulation of the SMC, inadequate maturation conditions, or inappropriate storage of the SMC, glass transport during molding is incomplete and the edges of the molded part show a lack of glass fibers which leads to unsatisfactory mechanical properties in the edge regions of the molded part or even breakages during demolding or deflashing. Too high a thickening level can also lead to problems as the cavity of the mold cannot be filled completely with the reinforced thermosetting resin during the molding process. The result are molded parts showing defects on their edges.
  • Initiators are radical forming substances that are stable up to a certain temperature. Above said temperature initiators decompose quickly. Derivatives of hydrogen peroxide wherein one or both hydrogen atoms are replaced by an organic group, e.g. di- tert -butyl peroxide and the like, are used most commonly. Up to the temperature of thermal decomposition only a small amount of free radicals is formed that can be scavenged by an inhibitor (see below). Above this temperature the rate of formation of free radicals is so high that the curing of the polyester or vinyl ester resin takes place via radical copolymerization of the double bonds in the resin and the reactive monomer.
  • inhibitors are used that can scavenge certain amounts of free radicals per time unit, thereby making it possible to adjust and guarantee the shelf life of the SMC.
  • the reactivity of the SMC and the height of the peak exotherm, i.e. the peak temperature reached during the curing process are also adjusted, thus making it possible to adjust the molding behavior in terms of mold flow and curing properties.
  • Internal mold release agents are used to facilitate demolding, i.e. removing the molded part from the hot mold. Mainly stearates of zinc (for lower molding temperatures) and calcium (for higher molding temperatures) or mixtures of both are used. In some cases also liquid mold release agents are used, some of them possessing also properties of process additives (cf. section 8 below).
  • the six ingredients described above basically constitute an SMC, i.e. a sheet of fibers impregnated with a thermosetting resin paste which has a surface that is not sticky and which can be cut into pieces and readily molded into parts of desired size, shape, and complexity.
  • SMC a sheet of fibers impregnated with a thermosetting resin paste which has a surface that is not sticky and which can be cut into pieces and readily molded into parts of desired size, shape, and complexity.
  • further ingredients can be used, namely:
  • fillers several desired properties can be introduced in the SMC.
  • One fundamental effect of the addition of fillers is a compensation of the shrinkage of the resin which is usually in the range of 8% to 10%, depending on the chemical nature of the resin (see above).
  • the inorganic filler does not take part in the polymerization reaction, it expands during molding due to the temperature of the mold or heat of reaction and adopts its former volume on cooling down after the molding process.
  • the fillers As the thermosetting resin is cross-linked at high temperature, the fillers partially act like a shrinkage compensating thermoplastic additive (see below), whereby they can improve the surface quality of the molded parts. Furthermore, fillers can also improve the mechanical properties of the finished parts. Nanofillers are fillers with a particle size below 100 nm; they can significantly improve the mechanical properties of molded parts although their homogenous dispersion in the resin is difficult to achieve and the viscosity of the resin may be influenced adversely. Other properties of the finished parts can also be achieved or adjusted with the help of fillers, e.g. conductive SMC can be made using conductive fillers like carbon black and the like. Fillers can be coarsely crystalline or finely comminuted (e.g., ground crystals or minerals). Most fillers, especially ground materials, possess a whitish color and lead to poor transparency of the SMC or the molded part.
  • a shrinkage compensating thermoplastic additive see below
  • This reaction has two important effects: Firstly, the compound is cooled by the vaporization of water and secondly, the flame is extinguished by the water vapor which lowers the oxygen concentration.
  • SMC can be filled with ATH to a very high degree which renders the SMC highly flame retardant.
  • Such flame retardant SMC can meet even the very demanding standards valid for railway industry like British Standard 6853 Class Ib or the new European Standard EN 45545.
  • Additives can perform very different tasks:
  • Shrinkage modifiers are thermoplastic materials generally divided into low shrink (LS) and low profile (LP) additives. Commonly, polymers such as e.g. polyethylene, polypropylene, polystyrene, saturated polyesters, polyvinyl acetate and the like are used. By thermal expansion during molding, thermoplastic additives lead to an increased surface quality in terms of smoothness as the cross-linking of the thermosetting resin "freezes" the expanded state in which the thermoplastics are at elevated temperature; thereby compensating the shrinkage of the pure resin and rendering the surface profile of the finished part more homogenous and free from sink marks or fiber print.
  • LS low shrink
  • LP low profile
  • Saturated polyesters in combination with polyvinyl acetates do not only compensate the shrinkage of the pure resin, they "overcompensate” shrinkage and lead to an expansion of up to 0.05%. This is a prerequisite for the use of such formulations for the molding of parts for car exterior application, known as Class-A materials.
  • Pigments usually in the form of pigment pastes, are used to produce colored SMC which can be molded to colored parts.
  • Important properties of pigment pastes are suitable particle size or particle size distribution of the pigments and good homogeneity of both the pigment paste itself and the colored resin paste, i.e. the thermosetting resin mixed with all fillers and additives and finally the color paste.
  • the coverage of the reinforcing fibers in the finished part has to be complete.
  • Pigment pastes to produce colored SMC are usually obtained by mixing pigment pastes of basic colors like red, yellow, blue, and black. With these mixtures e.g. most grey colors can be produced.
  • Pigment pastes are commercially available and are dispersions of suitable organic or inorganic pigments in non-thickenable carrier resins. Besides the chemical constitution of the pigments their physical properties like crystal form, particle size, and particle size distribution are of importance for their coloristic applicability and properties. Pigment producers try to obtain primary particles of optimum size and to inhibit agglomeration of these primary particles.
  • pastes of white pigments are used that are typically dispersions of ZnS and/or BaSO 4 pigments in non-thickenable carrier resins. These white pigment pastes are not always used, but in most cases they improve the appearance of the color, especially its homogeneity, brightness and purity. Moreover, the sizings of glass fibers tend to render the SMC somewhat yellowish and this effect is also partially overcome by the use of white pigment paste.
  • Particle sizes of the pigments are an important issue in connection with the color homogeneity. Typical particle sizes of commonly used pigments are given in terms of d 50 value in Table 1 below.
  • Table 1 Pigment Chemical Composition d 50 / ⁇ m Color White pigments ZnS/TiO 2 /BaSO 4 /2PbCO 3 ⁇ Pb(OH) 2 ⁇ 3
  • White Iron oxides Fe 2 O 3 /FeOOH 3-5 Yellow, orange, red, brownish Soot pigments soot, graphite, graphite dust ⁇ 1 Black, silver Lead chromates Pb 2 CrO 5 /PbCrO 4 1-3 Yellow, orange Spinel-type pigments CoAl 2 O 4 /Co(Al, Cr) 2 O 3 ⁇ 1 Blue, green, red, violet; yellow Organic pigments Phthalocyanines ⁇ 20 Blue, green
  • the basic ingredients of the SMC matrix i.e. thermosetting resin, thickening agent (unless added to the pigment paste, cf. below) and further optional ingredients such as initiator (curing agent), inhibitor (stabilizing agent), mold release agent, one or more fillers, additives or thermoplasts are mixed in a batch process in a mixer to form a resin paste.
  • the pigment paste which gives the SMC or the molded part its final color is usually prepared in a separate mixing process by mixing pigments pastes as explained above.
  • the thickening agent is preferably added to the pigment paste according to the formulation below.
  • the resin paste and the pigment paste containing the thickening agent are mixed on-line in a predetermined ratio in suitable static or dynamic mixers immediately before the production of the SMC.
  • the resulting mixture is pumped into a so-called doctor box which is a box with a slit on the lower side.
  • a carrier film e.g. of polyethylene or polyamide
  • the carrier film is then moving underneath a fiber cutter that cuts the continuous reinforcing fibers (rovings) into pieces of typically 25 mm to 50 mm length.
  • a second resin-covered carrier film is placed on the resin- and fiber-covered first carrier film to form a sandwich like sheet of a resin-impregnated fiber mat.
  • This sheet is finally moved through a compacting unit where the impregnation of the fibers is improved by the pressure applied by the rollers of the compacting unit.
  • the SMC is wound onto rolls or folded into cardboard boxes and stored in a controlled environment for maturation which usually takes several days, depending on the formulation. Maturation means here the thickening process which leads to a cuttable, non-sticky and easy to handle sheet of fiber reinforced thermosetting resin where the carrier film can be removed without resin sticking to the film.
  • Maturation means here the thickening process which leads to a cuttable, non-sticky and easy to handle sheet of fiber reinforced thermosetting resin where the carrier film can be removed without resin sticking to the film.
  • SMC sheets are cut into pieces of suitable size and shape, depending on the mold or part size. To achieve reproducible properties in the molded part the dimension and the weight of the sheets have to be kept constant. After removal of the carrier film(s) the sheets are put into the mold and the mold is closed.
  • the molding temperature is usually between 135 and 155 °C and the molding pressure between 30 and 100 bar, depending on the size and complexity of the mold or part.
  • the mold flow properties of the SMC itself also have a strong influence on the required molding pressure.
  • the molding time is usually in the range of a few minutes, however very "fast" SMC formulations can be cured within e.g. 50 seconds and for very thick parts up to 10 minutes molding time can be necessary.
  • Molds that can stand these conditions have to be made from steel; usually they are chrome-plated to facilitate demolding and to increase the surface quality of the finished parts. If the production numbers are less than e.g. 10 000 molded parts per year molds made of plastic, in particular thermosetting resins, can be used. Since these molds can only stand lower pressures as compared to standard steel molds, it is desirable to have sheet molding compounds which can be molded at e.g. 10 bar or even lower pressures. Sheet molding compounds suitable for these processing conditions are described in WO 99/50341 .
  • Alkaline earth oxides or hydroxides like magnesium oxide or magnesium hydroxide which are commonly used as thickening agents as described above tend to render the SMC opaque and blurred, which makes them incompatible with the use of luminescent pigments which require a transparent compound to be effective.
  • a self-luminescent SMC and articles molded therefrom can be obtained which exhibit a luminescence that is strong and long-lasting enough to meet the requirements which have to be fulfilled by articles like firemen's helmets.
  • the luminescent properties, i.e. strength and duration of afterglow, of such products are usually measured according to German standard DIN 67510.
  • the main problem is to keep the heavy luminescent pigments in suspension and to avoid sedimentation during storage and application. Phase separation between pigments and resin paste may also occur in standard (non-luminescent) SMC during maturation and storage if the physicochemical properties of the pigments and the resin are not compatible.
  • the luminescent pigments used in the present invention in spite of their particles being coarser (cf. below) and heavier than those of conventional pigments - are not prone to phase separation in the SMC. It appears that the thickening reaction of the polyester, which is anyway necessary in order to achieve satisfactory applicability and mold flow properties of the SMC, helps in avoiding phase separation of the pigment and the resin.
  • the present invention provides a luminescent molding compound, in particular a luminescent sheet molding compound.
  • a luminescent sheet molding compound As mentioned above several fundamental facts appear to be prohibitive to such a luminescent Sheet Molding Compound:
  • the volume of one particle of luminescent pigment LSW N1/SL is higher by a factor of 9.3 3 0.5 3 ⁇ 6435 , i. e. the number of particles in the same volume is in the luminescent pigment LSW N1/SL lower by a factor of 6435 compared to a conventional pigment with a particle size of 1 ⁇ m.
  • this factor is 15625 and with a pigment having a particle size of 34 ⁇ m even 39304. Nevertheless, it was now found that with pigments possessing such particle sizes it is possible to obtain a homogenously pigmented SMC and molded parts thereof.
  • a high solubility of the sizing of the glass fibers has a positive influence on the defilamentation of the fibers in the SMC, thus contributing to a homogeneous color of the SMC, especially when it is impossible to use white pigment pastes.
  • mold flow properties and the ventilation of the material during molding are affected adversely which may lead to air inclusions worsening transparency and luminescence and generally leading to rejection of the material by the customer. The above shows that there are contradictory demands on the behavior of glass fibers in a luminescent SMC.
  • Thickening agents are commonly dispersions of alkaline earth oxides and hydroxides like e.g. MgO or Mg(OH) 2 . These dispersions are whitish and are rendering the SMC and the molded part blurred if no other colored or white pigments are used.
  • MgO or Mg(OH) 2 alkaline earth oxides and hydroxides like e.g. MgO or Mg(OH) 2 .
  • These dispersions are whitish and are rendering the SMC and the molded part blurred if no other colored or white pigments are used.
  • As a certain transparency was expected to be necessary to make a satisfactory use of the photoluminescent pigments - especially in terms of pigments being embedded in deeper layers of the material - it was expected that the use of thickening agent would spoil the afterglow of the pigment and the material would not meet the standards in terms of strength and duration of afterglow.
  • thermoplastic additives for the compensation of the shrinkage of the pure resin was also expected to lead to problems as these thermoplastic additives are also very often rendering the compound or molded part whitish and blurred.
  • fillers which are necessary for two reasons as explained above. Firstly, fillers like aluminum trihydroxide are mandatory if the material has to be fire retardant. Secondly, fillers in general act as shrinkage compensation. As fillers are generally intransparent they have been expected to substantially decrease the duration and in particular the strength of afterglow. Especially the amount of fillers required to render the material sufficiently fire retardant for the production of equipment for fire brigades and the like was expected to decrease the afterglow to a level where molded part do not meet the standards for safety equipment.
  • a luminescent molding compound comprising
  • the luminescent molding compound is a sheet molding compound (SMC).
  • thermosetting resin is preferably an unsaturated ISO/NPG resin, i.e., a polyester resin based on isophthalic acid and neopentyl glycol.
  • the transparent reinforcing fibers are preferably assembled E glass rovings, i.e., rovings consisting of several bundles of E glass fibers.
  • the at least one photoluminescent pigment is preferably a long afterglow phosphorescent pigment or a mixture comprising at least one long afterglow phosphorescent pigment.
  • the photoluminescent pigments can be used in powder form or as a pigment paste comprising the photoluminescent pigment and a non-thickenable carrier resin, as mentioned above. Even sedimentation of the pigments in the pigment paste is not an issue in spite of the luminescent pigment being heavy. Anti-separation additives and the fact that the concentration of the pigments in the paste is high are obviously helpful in avoiding phase separation.
  • the at least one thickening agent comprises magnesium oxide and/or magnesium hydroxide.
  • the luminescent molding compounds comprise one or more fillers comprising aluminum hydroxide and/or calcium carbonate.
  • Another object of the invention is a luminescent article obtainable by molding and curing the luminescent molding compound of the invention.
  • a preferred embodiment of the luminescent article of the invention is a part of the equipment of fire brigades, police, or safety personnel, e.g. a firemen's helmet, tools, carriers of compressed air bottles, or other safety equipment.
  • luminescent article of the invention is a part of an electrical appliance or fitting, such as the housing of a lamp, a button, rocker or toggle of a switch, or a fuse box (breaker panel). Passive safety in buildings can be improved by the use of such article which is luminescent in the case of a power loss or damage of illuminant.
  • luminescent article of the invention is a part of a means of public or private transportation such as an automobile, taxi, bus, train, subway, ferry, aircraft etc., e.g. the handles in the inside of the trunk of a car.
  • a means of public or private transportation such as an automobile, taxi, bus, train, subway, ferry, aircraft etc.
  • the handles in the inside of the trunk of a car e.g. the handles in the inside of the trunk of a car.
  • it is imaginable to produce certain parts from a luminescent SMC to provide luminous parts in the case of an emergency situation.
  • luminescent SMC is especially interesting when luminescent properties are necessary due to safety demands, high mechanical properties, and/or flame retardance is necessary. This combination of demands can be fulfilled in a perfect way by the material described in the present invention.
  • a typical luminescent SMC formulation is given in Table 4 below.
  • Table 4 Ingredient Weight/kg Type Resin 4.000 Iso/NPG resin 1) Filler 2.500 Aluminum trihydroxide 2) Thermoplast 1.000 Polystyrene 3) Release agent 0.075 Zinc stearate Initiator 1 0.060 Slow curing agent 4) Initiator 2 0.020 Fast curing agent 5) Inhibitor 0.020 p -Benzoquinone (10% solution in MEK/styrene) Thickening Agent 0.125 Magnesium oxide paste 6) Pigment 1.800 Luminescent pigment 7) Additive 0.225 Mold release additive 8) Reinforcement 40% *) Glass fiber 9) *) Glass content given as weight percent of complete formulation 1) e.g.
  • Distitron ® SP 184 (Lonza), Distitron ® 170 (Lonza) or Palatal ® A 410-TV25 (DSM) 2) e.g. Martinal ® OL 104 (Martinswerk), Martinal ® ON 921 (Martinstechnik) or Portaflame ® SG 40 (Ankerpoort) 3) e.g. Empera ® 622 (BP Chemicals), Lacqrene ® 6541 (Total Petrochemicals) or Palapreg ® H814-01 (DSM) 4) e.g.
  • LUPEROX ® K12 MEK peroxide, Atofina/Arkema) or TBPB (tert-butyl perbenzoate, Degussa Initiators)
  • LUPEROX ® K18 MEK peroxide, Atofina/Arkema
  • TBPEH-LA-M2 Tert- butyl peroxy-2-ethylhexanoate, Degussa Initiators
  • Luvatol ® MK 35, Luvatol ® DH 25 or Luvatol ® EH 35 all Lehmann & Voss
  • Leutalux ® N1 Grün/S Leuchtstoffwerk GmbH Heidelberg
  • Lumilux ® SN-F2 Honeywell
  • Samcolux ® PLT Type 6 Samco) 8
  • P 9061 BYK-Chemie
  • P227/2400 tex Saint-Gobain Vetrotex
  • P243/2400 tex Saint-Gobain Vetrotex
  • 5249/2400 tex Saint-Gobain Vetrotex
  • R07E XI 2400 tex Owens Coming
  • the classification of the luminescence of a firemen's helmet which is necessary to fulfill German Industry Standard 67510 is 10/1,1-140 W/K.
  • the material described in this example is superior to this value.
  • German Industry Standard DIN 67510 luminescent behavior is measured as follows: The luminescent articles are kept in the dark for 48 h to ensure a complete loss of luminescent properties. Afterwards samples of 50x50 mm 2 are illuminated with a density of luminous flux (illuminance) of 1000 lux for five minutes. The emission is recorded for two hours and time until a density of luminous flux of 0.3 mcd/m 2 is reached is extrapolated.
  • the luminescence of the formulation described here which is given by the value 12.05/1.65-270 W/K means:
  • Distitron ® SP 184 (Lonza), Distitron ® 170 (Lonza) or Palatal ® A 410-TV25 (DSM) 2) e.g. Martinal ® OL 104 (Martinswerk), Martinal ® ON 921 (Martinswerk) or Portaflame ® SG 40 (Ankerpoort) 3) e.g. ALOLT 38 AF (Magyar Aluminium) or Martinal ON 310 (Martinswerk) 4) e.g. H1682 (DuPont) or Microthene ® FN 519-00 (Equistar Chemicals) 5) e.g.
  • Leutalux ® N1 Grün/SL Leuchtstoffwerk GmbH Heidelberg
  • Lumilux ® SN-F2 Honeywell
  • Samcolux ® PLJ Type 6 Samco (Samco) 9
  • P227/2400 tex Saint-Gobain Vetrotex
  • P243/2400 tex, bundle tex 17 or 34 Saint-Gobain Vetrotex
  • 5249/2400 tex Saint-Gobain Vetrotex
  • R07E XI 2400 tex Owens Coming
  • Distitron ® SP 184 (Lonza), Distitron ® 170 (Lonza) or Palatal ® A 410-TV25 (DSM) 2) e.g. Martinal ® OL 104 (Martinswerk), ALOLT 38 AF (Magyar Aluminium) or Portaflame ® SG 40 (Ankerpoort) 3) e.g. Micro Mica W1 (Micro Minerals) or Sachtosperse ® HUD (BaSO 4 , Sachtleben Chemie) 4) e.g. Empera ® 622 (BP Chemicals), Lacqrene ® 6541 (Atofina) or Palapreg ® H814-01 (DSM) 5) e.g.
  • LUPEROX ® K12 MEK peroxide, Atofina/Arkema) or TBPB ( tert -butyl perbenzoate, Degussa Initiators)
  • LUPEROX ® K18 MEK peroxide, Atofina/Arkema
  • TBPEH-LA-M2 tert -butyl peroxy-2-ethylhexanoate, Degussa Initiators
  • Luvatol ® MK 35, Luvatol ® DH 25 or Luvatol ® EH 35 all Lehmann & Voss
  • Leutalux ® N1 Grün/SL Leuchtstoffwerk GmbH Heidelberg
  • Lumilux ® SN-F2 Honeywell
  • Samcolux ® PLJ Type 6 Samcolux ® 9
  • DualGlo ® JTE5585 yellow pigment DiGlo Ltd.
  • Lumilux ® effect sipi yellow Honeywell
  • P 9061 BYK-Chemie
  • the firemen's helmet possesses a high visibility also in a bright environment, i.e. in normal daylight.
  • the afterglow however is not affected adversely.
  • the strength and duration of afterglow in comparison to a firemen's helmet with luminescent paint which is commercially available is given in Fig. 5.
  • the strength and duration of afterglow is much better (by a factor of approximately 4) in the firemen's helmet produced from luminescent SMC which increases safety of firemen in working situations with poor illumination as they can be seen by colleagues from a higher distance in the dark or e. g. in working conditions where there is a lot of smoke.
  • Characterization of the luminescent behavior is 86,6/11,2-1118W/K for the helmet from luminescent SMC and 21/2,3-295W/K for the painted helmet.
  • the mechanical properties of SMC for firemen's helmets are given in Table 7 below.
  • the non-luminescent formulation EJ 31508 fulfills German Industry Standard DIN EN 443.
  • the luminescent formulations EJ 32095 and EJ 32106 that have not been tested for their luminescent properties are superior to EJ 31508 in terms of mechanical properties.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP06002045A 2006-02-01 2006-02-01 Formmassen mit lumineszierenden Pigmenten Withdrawn EP1816178A1 (de)

Priority Applications (2)

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EP06002045A EP1816178A1 (de) 2006-02-01 2006-02-01 Formmassen mit lumineszierenden Pigmenten
PCT/EP2007/000869 WO2007088055A1 (en) 2006-02-01 2007-02-01 Molding compounds containing luminescent pigments

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EP06002045A EP1816178A1 (de) 2006-02-01 2006-02-01 Formmassen mit lumineszierenden Pigmenten

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Cited By (11)

* Cited by examiner, † Cited by third party
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WO2008062231A2 (en) * 2006-11-23 2008-05-29 Curon Limited Improvements in or relating to polymer composites
KR100886622B1 (ko) 2007-03-19 2009-03-04 주식회사 대주씨에스 형광 비엠씨 타일의 제조방법
WO2010085758A3 (en) * 2009-01-23 2010-09-30 Magna International Inc. Hvac components with anti-microbial properties
WO2011146136A2 (en) * 2010-05-20 2011-11-24 Polymer Dynamix, Llc Compounded masterbatch for carrying flame retardant materials and processes for preparing
WO2014030089A1 (en) * 2012-08-23 2014-02-27 Koninklijke Philips N.V. Stabilized wavelength converting element
ITAN20120156A1 (it) * 2012-11-26 2014-05-27 Piergiovanni Biagiotti Prodotto luminescente e relativo metodo di produzione.
RU2615374C1 (ru) * 2015-11-13 2017-04-04 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Эпоксивинилэфирное связующее, препрег и изделие из него
CN110075767A (zh) * 2019-04-18 2019-08-02 天津大学 长余辉水凝胶及制备方法
US10400165B2 (en) 2015-10-09 2019-09-03 Toray Industries, Inc. Color conversion composition, color conversion sheet and light source unit including the same, display, lighting apparatus, backlight unit, LED chip, and LED package
CN114316684A (zh) * 2021-12-24 2022-04-12 北京印刷学院 发光油墨及其制备方法、无机电致发光器件
CN115135474A (zh) * 2020-03-19 2022-09-30 Dic株式会社 片状模塑料和成形品的制造方法

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NZ591684A (en) * 2008-08-12 2012-12-21 Visual Signals Ltd Glow in the dark buoyant articles comprising inorganic photoluminescent material distributed through a polymer
US10836959B2 (en) 2015-05-26 2020-11-17 Toray Industries, Inc. Pyrromethene-boron complex, color-changing composition, color-changing film, light source unit including same, display, and lighting
US10800970B2 (en) * 2015-07-17 2020-10-13 Toray Industries, Inc. Color conversion composition, color conversion film and backlight unit, display and lighting device each comprising same
RU2608892C1 (ru) * 2015-11-13 2017-01-26 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Полиэфирное связующее и изделие на его основе

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008062231A3 (en) * 2006-11-23 2008-07-10 Curon Ltd Improvements in or relating to polymer composites
GB2456279A (en) * 2006-11-23 2009-07-15 Curon Ltd Improvements in or relating to polymer composites
WO2008062231A2 (en) * 2006-11-23 2008-05-29 Curon Limited Improvements in or relating to polymer composites
KR100886622B1 (ko) 2007-03-19 2009-03-04 주식회사 대주씨에스 형광 비엠씨 타일의 제조방법
WO2010085758A3 (en) * 2009-01-23 2010-09-30 Magna International Inc. Hvac components with anti-microbial properties
WO2011146136A2 (en) * 2010-05-20 2011-11-24 Polymer Dynamix, Llc Compounded masterbatch for carrying flame retardant materials and processes for preparing
WO2011146136A3 (en) * 2010-05-20 2012-04-12 Polymer Dynamix, Llc Compounded masterbatch for carrying flame retardant materials and processes for preparing
US9803809B2 (en) 2012-08-23 2017-10-31 Philips Lighting Holding B.V. Stabilized wavelength converting element
WO2014030089A1 (en) * 2012-08-23 2014-02-27 Koninklijke Philips N.V. Stabilized wavelength converting element
ITAN20120156A1 (it) * 2012-11-26 2014-05-27 Piergiovanni Biagiotti Prodotto luminescente e relativo metodo di produzione.
US10400165B2 (en) 2015-10-09 2019-09-03 Toray Industries, Inc. Color conversion composition, color conversion sheet and light source unit including the same, display, lighting apparatus, backlight unit, LED chip, and LED package
RU2615374C1 (ru) * 2015-11-13 2017-04-04 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Эпоксивинилэфирное связующее, препрег и изделие из него
CN110075767A (zh) * 2019-04-18 2019-08-02 天津大学 长余辉水凝胶及制备方法
CN115135474A (zh) * 2020-03-19 2022-09-30 Dic株式会社 片状模塑料和成形品的制造方法
CN115135474B (zh) * 2020-03-19 2024-04-16 Dic株式会社 片状模塑料和成形品的制造方法
CN114316684A (zh) * 2021-12-24 2022-04-12 北京印刷学院 发光油墨及其制备方法、无机电致发光器件

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